Htoroxyaijphatic thioammeiine



I Q tented Apr. 8, 19 41 'iTEo Herman A, Bruson, Philadelphia, Pa.,assimor to The Resinous Products & Chemical Company,

Philadelphia, Pa.

No Drawing. Application August 19, 193i,

Serial No. 291,012

o Cls. (cl. eta-2n) This invention deals with hydrouyaliphatic ethers olthioamrncline and relates more particularly to the preparation of newcompounds haviny a hydroryor polyhydroxy-aliphatlc group of at least twocarhon atoms attached to the sulfur atom at thioaeline.

This application is ,a continuation-in-part oi rny copending applicationSerial No. 283,740, filed ululy ll, rose,

hn ohiect of this invention is to make available thioamineline etherswhich possess a reactive hydroryl uroun, rmitting reaction not only" orthe tria'aine group with aldehydes hut oi the hydroryl arena with suchreagents as acids to tor esters or trithother hydroryl-hearing compounds to lorin others. It is also obje t to provide compounds usefultor the preparation of ethers oi thioammeline are obtained by condensingthioacline in alkaline solution with a member of the group consisting ofaiitylene halohydrins and polyalkylene ether halohydrins having at leasttwo carbon atoms in each alirylene group.

ical compounds of this group include ethylene chlorohydrin, propylenechlorohydrin, isohutylene chlorohydrin, glycerol monochlorohydrin,glycerol dlchlorohydrin, p-methylglycerol chlorohydrin, diethyleneglycol chlorohydrin, triethylene glycol chlorohydrin, epichlorohydrin,pinethylepichlorohydrin, and higher homologues thereof, or with thecorresponding bromohydrins. There may also be used the polyethyleneglycol chiorohydrins having from about to about 10 alhylene groupstherein.

The condensation of one of the above coinpods and thioammellne takesplace readily in the presence ofa water-soluble alkaline, acidhindingagent. In the preferred form of this inventlon thioammeline is dissolvedin an aqueous other cases heat is required. In either event the reactionis accelerated by heating the mixture for several hours or more withrapid stirring. Heating under reilua at -1100" C. is most con" venientbut higher temperatures may he used it heating is conducted underpressure. in practically all cases the product may be separatedincrystalline or solid form. The products ohtained are particularlyvaiuahle intermediates tor the preparation of resins which they giveupon condensatlon with an aldehyde, such as iormalde hyde. They may beused in conjunction with urea, thiourea, melamine, and other methylolforming compounds to improve the properties oi: resins termedtherelron'i. They may also he es terirled with organic or inorganicacids, acid all hydrides or acid chlorides to give compounds use iui astextile assistants, plasticizers, insecticides, or dye intermediates.They may be reacted with both an aldehyde and a resin-romaine,polycarboxylic acid or a drying or non-drying, iatty acid 7 to giveresinous products for use in varnishes, lacquers, enamels, etc. and foruse in conjunction with other resins, such as urea-iormaldehyde,phenol-formaldehyde, etc. to which they impart improvedwater-resistance, plasticity, and other desirable properties. Thecondensates formed from the hydroxyaliphatic ethers of thioanimeline,formaldehyde, and a hydroxyl-bearing compound, such asbutyl alcohol,octyi alcohol, glu cose, glycerine or a compound related to these, areof particular value as solvent-soluble resins ,with some degree ofthermoplasticity. also, the hydroxyaliphatic ethers oi thioammeline mayhe reacted with an aldehyde in the presence oi hoth an alcohol and anacid. These ethers themselves are useful in the form of theirwater-soluble or oil-soluble salts as bactericicles, insecticides,vulcanization accelerators, additives ior lubricating andrust-preventive compositions, etc.

' The hydroxyaliphatic others of thioammeline may be represented by theformula rying a hydroxyl group and having at least two carbon atomsbetween the sulfur atom and an oween atom and between successive oxygenatoms.

The following examples illustrate this invention:

Eznampie i To a clear. filtered solution of 28.6 g. at thio= ammeline, sg. of sodium hydroxide and soc cc. of water heated to 90 C. there wasadded grad= ually with stirring 16.1 g. of ethylene chlorohy drin. Themixture was stirred at this temperature for five minutes and was thencooled and allowed to stand. After standing for as hours, 32 g. ofcolorless crystals separated. 'ihiaprod not upon recrystallization fromhot water sepia.=

rates in colorless needles, M. P. 185-188 6., the

analysis of which corresponds to the formula NHs c-s-cniolmon NH:

Example 2 To a clear, filtered solution of 28.6 g. of thi ammeline, 8 g.of sodium hydroxide, and 300 cc. of water there was added all at once at901 C. 19 g. of propylenechlorohydrin with rapid stirring. After themixture was heated at 90-95 C. for 10 minutes. the hot solution wasfiltered. On cooling, the hydroxy propylthioammeline separated incolorless crystals which upon recrystal lization from water melted at179-180" C.-

Example 3 Twenty-six grains of isobutylene chlorohydrin was added to aclear, filtered solution of 8 g. of sodium hydroxide, 300 'cc. of water,and 28.6 3. of thioammeline. The mixture was stirred and heated to 90-95C. for 30-40 minutes. The crystals which separated after standing for 24hours weighed 32.5 3. After recrystallization from water they formedcolorless prisms, M. P. 195-196 C., the analysis of which corresponds tothe formula CH N/ Example 4 ,To a clear, filtered solution of 14.3 g.oithioammeline, 4' g. of sodium hydroxide and 150 cc. of water there wasadded 10.5 g. of trimethylene chlorohydrin. The mixture was stirred andheated at 90-95 C. for 30-40 minutes. After it had stood 18 hours, therewas obtained 15.8 8. of solid product which after recrystallization fromwater formed colorless crystals, M. P.

173-175" 0., the analysis of which corresponds to the formula NH: 2 K N+s-cmomomon Example 5 To a clear solution of 28.6 g. of thioammeline, 8z. of sodium hydroxide, and 275 cc. of water there was added 25 g. ofdiethylene glycol chloromas es 3 hydrin (@lCalI-ie-O-CziisGE-i) Themixture was stirred and heated at St C. for so minutes. After it hadstood 2 5 hours, $4.5 s. of solid product separa which uponrecrystallization from water formed colorless plates, ltd. P. 12 34 Q,the analysis of which corresponds to the formula 1. A hydroxyaliphaticether of thioammeline having the formula wherein A is a member of theclass consisting of (1) a saturated aliphatic carbon chain having atleast one hydroxyl radical and (2) a saturated aliphatic carbon chaininterrupted by oxygen, said chain carrying a hydyroxyl group and havingat; least two carbon atoms between the sulfur atom and an oxygen atomand between successive oxygen atoms. I

2. A hydroxyaliphatic thioether of ammeline having at least two carbonatoms in the aliphatic residue. 1

5:1. Hydroxyethyl thioammeline having the form a N o-s-culomon c= N lifls 4. Hydroxyethoxyethyl thioammeline having the formula & N v NC-S-CHsCHiOCHICHsOH C=N 111B:

5. Hydroxy-tertiary-butyl thioammeline having the formula t. A processwhich comprises condensing thioammeiine in alkaline solution with amember of the group consisting of alkylene halohydrins of at least twocarbon atoms and poiyalkylenc ether halohydrins having at least twocarbon atoms in each alkyiene group.

7. A process which comprises condensing thioammeline in a solution of analkali hydroxide with a member of the group consisting of atkylenehalohydrins of at least two carbon atoms in and polyalkyiene etherhalohydrins having at least two carbon atoms in each alkylene group.

8. A process which comprises condensing thicammeline in alkalinesolution with an alkyl ene chlorohydrin.

9. A process which comprises condensing thioammeline in alkalinesolution with ethylene chlorohydrin.

